Materials Chemistry and Physics 143 (2014) 728e734

Contents lists available at ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Reversed austenite in 0Cr13Ni4Mo martensitic stainless steels

Y.Y. Song a, *, X.Y. Li a, L.J. Rong a, Y.Y. Li a, T. Nagai b
a
Institute of Metal Research, Chinese Academy of Science, Shenyang 110016, China
b
National Institute for Materials Science, Sengen 1-2-1, Tsukuba 305-0047, Japan

h i g h l i g h t s

The amount of the reversed austenite formed at high temperature increases with the holding time.

STEM results directly show that carbon is mainly partitioned into the carbides and Ni into the reversed austenite.

The Ni enrichment and the ultrafine size are the main factors leading to the stabilization of the reversed austenite.

a r t i c l e i n f o a b s t r a c t

Article history: The austenite reversion process and the distribution of carbon and other alloying elements during
Received 11 April 2013 tempering in 0Cr13Ni4Mo martensitic stainless steel have been investigated by in-situ high temperature
Received in revised form X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM). The microstructure of
16 August 2013
the reversed austenite was characterized using transmission electron microscopy (TEM). The results
Accepted 2 October 2013
revealed that the amount of the reversed austenite formed at high temperature increased with the
holding time. Direct experimental evidence supported carbon partitioning to carbides and Ni to the
Keywords:
reversed austenite. The reversed austenite almost always nucleated in contact with lath boundary M23C6
Alloys
Electron microscopy
carbides during tempering and the diffusion of Ni promoted its growth. The Ni enrichment and the
Microstructure ultrafine size of the reversed austenite were considered to be the main factors that accounted for the
X-ray diffraction topography stability of the reversed austenite.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction (athermal martensite start temperature) on the austenite grain size

The martensitic steels with a fine dispersion of reversed or
retained austenite have attracted much attention for decades.
These steels present an excellent combination of strength and
ductility [1,2], for the reversed austenite will transform to
martensite during straining, bringing about the so called trans-
formation induced plasticity (TRIP) effect [3]. The presence and
stability of the reversed austenite at room temperature are of
critical importance for the occurrence of the TRIP effect. There are
four factors which are highly correlated to the stabilization of the
reversed austenite in these steels [4,5]. The first factor is the con-
centration of the strong austenite stabilizers, such as C, Ni, Mn and
so on [6e8]. A new development known as “quenching and parti-
tioning” (Q&P) has been proposed, in which the excess carbon is
allowed to partition into the austenite and stabilize it to ambient
temperature [9]. The second factor is the grain size of the reversed
austenite [10]. Yang et al. have confirmed the dependence of Ms
* Corresponding author. Tel.: þ86 24 23971985; fax: þ86 24 23978883.
E-mail address: songyuanyuan@imr.ac.cn (Y.Y. Song).
[11]. The third one is the dislocation density in austenite [12].
Krauss has reported that the stability of the reversed austenite is
due to the high concentrations of tangled and jogged dislocations
[13]. Bilmes et al. have considered that the stability of the reversed
austenite is due to its substructure [2]. The last one is the
morphology [5]. Recently, Xiong et al. have demonstrated that a low
carbon film-like austenite is more stable than the high carbon
blocky austenite [14]. In most cases, more than one factor de-
termines the stability of the reversed austenite [4,10].
Different heat treatments have been proposed to introduce the
reversed austenite for different martensitic steels. For the
martensitic stainless steels like 0Cr13Ni4Mo steels, maraging steels
like 13-8PH, and 9Ni steels, and so on, the conventional quenching
and tempering (Q&T) process has been effectively utilized [15e18].
The amount of the reversed austenite can be controlled by the
tempering temperature. As for the low carbon martensitic stainless
steel 0Cr13Ni4Mo in the present study, the previous investigations
by the authors have discussed the formation mechanism of the
reversed austenite in detail [7,16,19]. The reversed austenite can
only be obtained by tempering of the as-quenched martensite in
the temperature range of 580e650  C [16]. It has been proved that

0254-0584/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matchemphys.2013.10.006
 Y.Y. Song et al. / Materials Chemistry and Physics 143 (2014) 728e734 729

the Ni is enriched in the reversed austenite by means of three

dimensional atom probe (3DAP) and transmission electron micro-
scopy (TEM) equipped with energy dispersive X-ray spectroscopy
(EDS) [16]. The reversed austenite is found to bear a Kurdjumove
Sachs (KeS) orientation relationship (OR) with the martensite and
a cubeecube orientation relationship with the M23C6 carbides
[7,20,21]. It has been confirmed that the first step is the precipita-
tion of the M23C6 carbides along the martensite lath boundaries [7].
In 0Cr13Ni4Mo steels, the tempering temperatures (580e650  C)
are too low for the carbides to dissolve. It is thus not clarified that
how the carbon distribute in the reversed austenite and M23C6
carbides. Whether the carbon will enrich in the reversed austenite
is still obscure. In the present study, in-situ high temperature X-ray
diffractometer and scanning transmission electron microscopy
(STEM) equipped with EDS were employed to reveal austenite
reversion process and the elemental distribution in the reversed
austenite, the carbides and the martensitic matrix at nano-scale.
Microstructure of the reversed austenite during tempering was
characterized using transmission electron microscopy (TEM). In
addition, the factors influencing the stability of the reversed
austenite were discussed.

2. Materials and experimental methods

The studied material was a low carbon martensitic stainless steel

with a chemical composition of 0.051Ce12.34Cre3.86Nie0.45
Moe0.5Mne0.022Pe0.004S (wt.%), which was supplied as a hot-roll
sheet. Homogenized specimens were austenitized at 1050  C for 2 h
and then water quenched.
0.1 mm  10 mm  10 mm sized of the as-quenched samples
were prepared for in-situ high temperature XRD on a Bruker D8
Discover X-ray diffractometer using Cu Ka radiation. The integrated
intensities of the (110)g and (111)a were used to determine the vol-
ume fraction of the reversed austenite, which was calculated by the
equation reported elsewhere for the same steel [16]. The as-quenched
specimens were heated to the tempering temperature 580  C and
610  C at the rate of 1  C s1 and held for 5 mine90 min and XRD data
were obtained at each holding time respectively. Spectra were taken
in the range of 2q from 41.5 to 48 , with a step size of 0.4 .
The as-quenched samples were tempered at 570  C, 590  C and
610  C for 2 h respectively. Specimens of the as-tempered for STEM
and TEM analysis were prepared by means of a twin-jet polishing
technique using 6 vol% HClO4 ethanol electrolyte at low tempera-
ture. A JEOL 2100 with accelerating voltage of 200 kV was
employed. The analysis was performed with the microscope oper-
ating in STEM mode. The size of the focused electron beam was
about 1 nm in diameter. The dwelling time was chosen as 1 ms. A
JEM 2010 TEM operated at 200 kV was used to observe the
microstructure of the reversed austenite.

3. Results Fig. 1. In-situ high X-ray diffraction profiles during tempering at 580  C (a) and 610  C
(b) at different holding time; (c) the austenite volume fraction as a function of holding
3.1. In-situ high temperature XRD results time measured at 580  C and 610  C respectively.

Fig. 1 shows the amount of the reversed austenite vs. the holding
time at the tempered temperature of 580  C and 610  C respectively
measured by in-situ high temperature XRD. Diffraction peaks from
the reversed austenite are clearly visible in the samples tempered for
15 mine90 min, as shown in Fig. 1a and b. However, no austenite
peak was observed for the sample tempered at 580  C for 5 min and
a weak peak can be seen in the sample tempered at 610  C. The
reason may be that the amount of the reversed austenite is below the
detection limit of XRD. Fig. 1c shows the phase fraction of the
reversed austenite as the function of the holding time at 580  C and
610  C. It can be seen that the amount of the reversed austenite
increases with the holding time at both tempering temperature. The
amount of the reversed austenite changes with holding time at the
same aging temperature are mainly due to the result of the Ni
diffusion, which promotes the growth of the reversed austenite and
which will be discussed below.
3.2. TEM observations
Fig. 2a shows bright field TEM micrographs of the initial
microstructure of the as-quenched samples. The martensitic lath
730 Y.Y. Song et al. / Materials Chemistry and Physics 143 (2014) 728e734

Fig. 2. (a) Bright field TEM image of the as-quenched sample and (b) XRD pattern
obtained at room temperature.

structure is clearly visible in the sample. The average size is

approximately 200 nm wide. A high density of dislocation can be
observed in the martensite matrix. To determine the phases in the
as-quenched sample, X-ray diffraction experiments were con-
ducted. Only martensite phase peaks can be seen in Fig. 2b. The
XRD results indicate that the austenite transformed completely into
martensite during quenching. No retained austenite or carbide
precipitation was found in the as-quenched sample.
Fig. 3 shows a bright field TEM image of the sample tempered at
570  C for 2 h, together with the selected area electron diffraction
(SAED) pattern of the precipitation area marked by arrow. The Fig. 3. (a) Bright field TEM image of the sample tempered at 570  C for 2 h; (b) SAED
precipitation is indexed as M23C6 carbides based on the SAED pattern of the area marked by the arrow in (a).

pattern. This observation indicates that the nano-sized carbides

form firstly during tempering in the martensite lath boundaries.
Actually, the M23C6 carbide was in the KurdjumoveSachs OR with
the martensite matrix depending on the previous investigations by
the authors [7].
The TEM image taken from the sample tempered at 590  C for 2 h
is shown in Fig. 4. According to the SAED pattern (Fig. 4b), the
diffraction spots from the reversed austenite and the carbides can be
observed when compared to Fig. 3. There is a parallel OR between
M23C6 and the reversed austenite, named a cubeecube OR. This is in
agreement with the work of other researchers [21]. From Fig. 4a, it
can be seen that the reversed austenite coexist with the M23C6 car-
bide along the martensite lath boundary. The reversed austenite
can’t be distinguished from the M23C6 carbide by the morphology in
the bright field TEM image. This is due to that the reversed austenite
always formed in contact with the carbides and the lattice co-
herency, which has been discussed in detail previously [7].
Fig. 5 represents the TEM image and corresponding SAED
pattern of the sample tempered at 610  C. It indicates that the
reversed austenite and the M23C6 carbides are in a cubeecube OR
along the martensite lath boundary just as shown in Fig. 4. The dark
field TEM image of the carbides is shown in Fig. 5c. The bright
particles are the M23C6 carbides, and the adjacent areas are the
reversed austenite.
3.3. STEM observations
To understand the elemental distribution during tempering,
STEM was employed to characterize the chemical composition
changes between the carbides and the reversed austenite at nano-
scale. Fig. 6 displays a bright-field STEM image and the corre-
sponding EDS mappings of C, Mo, Ni and Cr respectively in the
specimen tempered at 590  C. Based on the previous results of the
morphology of the reversed austenite obtained by TEM, the
reversed austenite and the martensite matrix are distinguished in
the bright-field STEM image, as shown in Fig. 6a. The film-like
reversed austenite locates on the lath boundary of the martensite.
 Y.Y. Song et al. / Materials Chemistry and Physics 143 (2014) 728e734 731

Fig. 4. (a) Bright field TEM image of the sample tempered at 590  C for 2 h; (b) SAED pattern.

But it can’t be identified the carbides with the reversed austenite
from the morphology of the bright field image because the reversed
austenite always lies adjacent to the carbides. From Fig. 6b and c, it
can be seen that the C and Mo signals were not observed clearly in
the acquired EDS mapping. It is thought that the degrees of
enrichment of C and Mo enrichment are too low to be identified. On
the contrary, there are noticeable compositional distributions of Ni
and Cr among the reversed austenite and martensite. It should be
noticed that Ni is mainly segregated in the reversed austenite re-
gion. This is in agreement with the previous works of the authors
that the reversed austenite is enriched by Ni atoms [16]. Also, it has
been found by TEM that in the adjacent of the reversed austenite
there exist the carbides M23C6, in which M is indicated as strong
carbide-forming elements, such as Cr or Mo. So the Cr segregation
area shown in Fig. 6e can be represented as the carbides. To reveal
the distribution of Ni and Cr clearly, the outline sketches of the
segregation areas of the two elements are given in Fig. 6f. The Ni
segregation area could be regarded as the reversed austenite and
the Cr segregation area as the carbides. It can be seen that the
maximum size of the carbides are no more than 200 nm long and
that of the reversed austenite are no more than 500 nm long.
The bright-field STEM image and the corresponding EDS map-
pings of C, Mo, Cr and Ni of the sample tempered at 610  C are
shown in Fig. 7. A perfect distribution of the main components was
observed, especially the carbon distribution. The C and Mo signals
can obviously be seen in Fig. 7b and c. A careful comparison of the C,

Fig. 5. (a) Bright field TEM image of the sample tempered at 610  C for 2 h; (b) SAED pattern and (c) the dark field image taken from the M23C6 carbides.
732 Y.Y. Song et al. / Materials Chemistry and Physics 143 (2014) 728e734

Fig. 6. (a) STEM bright-field image from the sample tempered at 590  C. The EDS mapping of C, Mo, Ni and Cr are shown in (b), (c), (d) and (e) respectively and (f) is the outline
sketches of the Ni and Cr segregation area from (d) and (e).

Fig. 7. (a) STEM bright-field image from the sample tempered at 610  C. The EDS mapping of C, Mo, Ni and Cr are shown in (b), (c), (d) and (e) respectively and (f) is the outline
sketches of the Ni and Cr segregation area from (d) and (e).
 Y.Y. Song et al. / Materials Chemistry and Physics 143 (2014) 728e734
Cr and Mo in the EDS mappings suggests that C is totally correlated
with Cr and Mo, as shown in Fig. 7b, c and e. This illustrates that
almost all carbon are distributed together with Cr and Mo inside
the carbides. It can be seen clearly that the Ni are clearly partitioned
to the adjacent reversed austenite from Fig. 7d. The elemental
mappings imply that the Ni and C are present in separate domains.
The signals of C barely overlap with that of Ni. The outline sketches
for the Cr and Ni distributions were shown in Fig. 7f, where the Ni
segregation area corresponds to the reversed austenite and the Cr
segregation to the carbides. The average size of the carbides and
reversed austenite is larger than that in Fig. 6. It seems that Ni
diffused out from the carbides during tempering due to the for-
mation of carbide since the relatively strong affinity of Cr atoms for
C.
Fig. 8 shows the typical EDS spectra taken from the M23C6 car-
bide and the reversed austenite. It can be seen that the Cr and Mo
peaks from the carbide appear much stronger than that from the
reversed austenite but the Ni peak weaker. The atomic percentage
for Ni is 6.13% in the reversed austenite, which is much higher than
Fig. 8. EDS spectra taken from M23C6 carbide (a) and the reversed austenite (b) on one
site in the image of Fig. 7; (c) the table shows the EDS atomic percentages for Ni and Cr
from the carbide and the reversed austenite.
733
that in the M23C6 carbide and the matrix. Base on the STEM-EDS
data, it can be concluded that C partitioned to M23C6 carbides
with Cr and Mo, while Ni partitioned to the reversed austenite
during the tempering. The Ni enrichment plays an important role in
the formation and stability of the reversed austenite.
4. Discussion
4.1. Phase formation in 0Cr13Ni4Mo steels
0Cr13Ni4Mo steels have a good hardenability due to the high Cr
content. The microstructure is all martensite after quenched to the
room temperature. It is difficult to find the carbides or the retained
austenite in the as-quenched samples, as shown in Fig. 2. Thus, the
austenite observed after the tempering is the reversed austenite. Cr
is a strong carbide former element and has a high diffusion coef-
ficient in a-iron [22]. It can diffuse rapidly for the carbides to
nucleate when the tempering temperature is at 570  C. The M23C6
carbides are precipitated preferentially at the martensite lath
boundaries. The boundary sites are preferred because of the greater
ease of diffusion in these regions [22]. This means that in the
0Cr13Ni4Mo stainless steel, the M23C6 carbide precipitates are
typical because the processing is Q&T. The M23C6 carbides have a
limited solubility of Ni, which will extrude the Ni into the adjacent
area, providing the nucleate site and driving force for the austenite
reversion. Thus the reversed austenite are found to start at the
adjacent areas where the local Ni concentration is high enough and
the nucleation energy low enough to promote the formation of
austenite. The M23C6 carbide and the austenite have cubic sym-
metry, and the lattice parameter of M23C6 is approximately three
times than that of the austenite, so the electron diffraction patterns
are readily identified, giving the cubeecube OR invariably. The
preferred interface is like this: the {111} plane of the M23C6 contacts
with the {111} plane of the austenite [23]. Such a selection occurs to
minimize the interface energy. Thus the reversed austenite is al-
ways found to nucleate at the adjacent to the carbides. The STEM/
EDS results in this study indicate that the growth of the reversed
austenite is a process of partitioning. Fig. 7 confirmed that C par-
titioned into the carbides with Cr and Ni partitioned from the
matrix and the carbides into the reversed austenite, which illus-
trates that the reversed austenite grows by the Ni diffusion.
4.2. Stability of the reversed austenite
Carbon, which is well known to be a strong austenite stabilizer,
can result in high austenite stability at room temperature. However,
during tempering, the M23C6 carbides first precipitated along the
martensite lath boundaries as discussed before. The C is mainly
partitioned into the carbides. Thus C contributes little on the sta-
bilization of the reversed austenite. Due to the isothermal section of
the FeeCreNi phase diagram [24], more Ni content is necessary for
the austenite formation as the temperature decreases at the equi-
librium state. Depending on the results obtained by 3DAP and TEM/
EDS, the average concentration of Ni in the reversed austenite ob-
tained at room temperature in the range of 5%e11% [7,16]. It is
indubitable that it is the enrichment of Ni that play the major role in
the formation and stabilization of the reversed austenite.
However the Ms calculated in term of the reversed austenite
composition is 28  C, which is not accurately in agreement with
subzero treatment results [19]. Previous works of the authors have
shown that the reversed austenite can keep stable at the liquid
helium temperature and not transform to the martensite [19]. This
indicates that the chemical composition of the reversed austenite is
not the only reason for its stability. According to the results above
and the previous results, the reversed austenite always coexists
734 Y.Y. Song et al. / Materials Chemistry and Physics 143 (2014) 728e734

with the carbides as a whole. The ultrafine carbides are dispersed in References
the matrix, which determines the formation of the ultrafine
reversed austenite. Based on the works by the authors, a statistical [1] H. Nakagawa, T. Miyazaki, J. Mater. Sci. 34 (1999) 3901.
[2] P.D. Bilmes, M. Solari, C.L. Llorente, Mater. Charact. 46 (2001) 285.
comparison of the reversed austenite shows that the length of the [3] V.F. Zackay, E.R. Parker, D. Fahr, R. Busch, Trans. ASM 60 (1967) 252.
reversed austenite is in the range of 100e500 nm. Therefore, it is [4] S. Lee, S.J. Lee, B.C. De Cooman, Scr. Mater. 65 (2011) 225.
considered that the ultrafine size of the reversed austenite is also a [5] I. Timokhina, P. Hodgson, E. Pereloma, Metall. Mater. Trans. A 35A (2004)
2331.
factor leading to the stabilization of the reversed austenite. [6] S. Lee, S.J. Lee, B.C. De Cooman, Scr. Mater. 64 (2011) 649.
[7] Y.Y. Song, X.Y. Li, L.J. Rong, D.H. Ping, F.X. Yin, Y.Y. Li, Mater. Lett. 64 (2010)
5. Conclusions 1411.
[8] L. Yuan, D. Ponge, J. Wittig, P. Choi, J.A. Jimenez, D. Raabe, Acta Mater. 60
(2012) 2790.
In summary, the austenite reversion evolution and elemental [9] J. Speer, D.K. Matlock, B.C. De Cooman, J.G. Schroth, Acta Mater. 51 (2003)
distribution of the reversed austenite in 0Cr13Ni4Mo martensitic 2611.
[10] E. Jimenez-Melerp, N.H. van Dijk, L. Zhao, J. Sietsma, S.E. Offerman, J.P. Wright,
stainless steel were investigated using in-situ high temperature
S. van der Zwaag, Scr. Mater. 56 (2007) 421.
XRD and TEM. The results indicated that the carbon was mainly [11] H.S. Yang, H.K.D.H. Bhadeshia, Scr. Mater. 60 (2009) 493.
partitioned into the carbides and the Ni into the reversed austenite. [12] J. Mahieu, J. Maki, B.C. De Cooman, S. Claessens, Metall. Mater. Trans. A 33A
(2002) 2573.
M23C6 carbides firstly precipitated at the original martensitic lath
[13] G. Krauss, Acta Metall. 11 (1963) 499.
boundaries, which supplied the nucleation sites for the reversed [14] X.C. Xiong, B. Chen, M.X. Huang, J.F. Wang, L. Wang, Scr. Mater. 68 (2013)
austenite formation. The Ni enrichment at the reversed austenite 321.
and carbide boundaries provided the driving force for the austenite [15] R. Schnitzer, R. Radis, M. Nohrer, M. Schober, R. Hochfellner, Mater. Chem.
Phys. 122 (2010) 138.
reversion. The reversed austenite grew by the Ni diffusion. The Ni [16] Y.Y. Song, X.Y. Li, L.J. Rong, Y.Y. Li, Mater. Sci. Eng. A 528 (2011) 4075.
enrichment and the ultrafine size were considered to be the main [17] C.K. Syn, B. Fultz, J.W. Morris Jr., Metall. Trans. A 9A (1978) 1635.
factors leading to the stabilization of the reversed austenite. [18] W.M. Garrison, J.A. Brooks, Mater. Sci. Eng. A 149 (1991) 65.
[19] Y.Y. Song, D.H. Ping, F.X. Yin, X.Y. Li, Y.Y. Li, Mater. Sci. Eng. A 527 (2010)
614.
Acknowledgments [20] G.V. Kurdjumov, G.Z. Sachs, Z. Physik 64 (1930) 325.
[21] P.H. Pumphrey, J.W. Edington, Acta Metall. 22 (1974) 89.
[22] R.W.K. Honeycombe, H.K.D.H. Bhadeshia, Steels e Microstructure and Prop-
The authors gratefully acknowledge the support of the funding erties, Edward Arnold, London, 1995.
by Natural Science Foundation of China (no. 5087111 and no. [23] M.H. Lewis, B. Hattersley, Acta Metall. 13 (1965) 1159.
51201162). [24] V. Raghavan, J. Phase Equilib. 24 (2003) 261.